Heterolytic bond scission is a staple of chemical reactions. While qualitative and quantitative models exist for understanding the thermal heterolysis of carbon-leaving group (C-LG) bonds, no general models connect structure to reactivity for heterolysis in the excited state. CASSCF conical intersection searches were performed to investigate representative systems that undergo photoheterolysis to generate carbocations. Certain classes of unstabilized cations are found to have structurally nearby, low-energy conical intersections, whereas stabilized cations are found to have high-energy, unfavorable conical intersections. The former systems are often favored from photochemical heterolysis, whereas the latter are favored from thermal heterolysis. These results suggest that the frequent inversion of the substrate preferences for nonadiabatic photoheterolysis reactions arises from switching from transition-state control in thermal heterolysis reactions to conical intersection control for photochemical heterolysis reactions. The elevated ground-state surfaces resulting from generating unstabilized or destabilized cations, in conjunction with stabilized excited-state surfaces, can lead to productive conical intersections along the heterolysis reaction coordinate. Disciplines Materials Chemistry | Other Chemistry | Physical Chemistry CommentsReprinted (adapted) with permission from J. Am. Chem. Soc., 2014, 136 (25) ABSTRACT: Heterolytic bond scission is a staple of chemical reactions. While qualitative and quantitative models exist for understanding the thermal heterolysis of carbon−leaving group (C−LG) bonds, no general models connect structure to reactivity for heterolysis in the excited state. CASSCF conical intersection searches were performed to investigate representative systems that undergo photoheterolysis to generate carbocations. Certain classes of unstabilized cations are found to have structurally nearby, low-energy conical intersections, whereas stabilized cations are found to have high-energy, unfavorable conical intersections. The former systems are often favored from photochemical heterolysis, whereas the latter are favored from thermal heterolysis. These results suggest that the frequent inversion of the substrate preferences for nonadiabatic photoheterolysis reactions arises from switching from transition-state control in thermal heterolysis reactions to conical intersection control for photochemical heterolysis reactions. The elevated ground-state surfaces resulting from generating unstabilized or destabilized cations, in conjunction with stabilized excited-state surfaces, can lead to productive conical intersections along the heterolysis reaction coordinate.

We report an organo-paramagnetic switch consisting of a linked bis(viologen) dication diradical that can be cycled reversibly between diamagnetic and paramagnetic states via noncovalent guest-host chemistry with cucurbit [7]uril (CB[7]) in room-temperature water. Computations suggest that the nature of the interaction between the viologen cation radical units is that of a pi dimer (pimer). Molecules with switchable magnetic properties have possible applications in spintronics, data storage devices, chemical sensors, building blocks for materials with switchable bulk magnetic properties, as well as magnetic resonance probes for biological applications. DisciplinesOrganic Chemistry | Other Chemistry | Physical Chemistry CommentsReprinted (adapted) with permission from J. Am. Chem. Soc., 2013, 135 (29) O rganic molecules with magnetic properties hold promise

A polymer containing viologen radical cation monomer units is shown to reversibly switch between paramagnetic and diamagnetic states via non-covalent host-guest interactions or temperature control in water. Cycling between diamagnetic and paramagnetic forms is accompanied by changes in optical and magnetic properties.